CN115000387B - Spinel type TM-HEO/C composite material, preparation method and application - Google Patents

Spinel type TM-HEO/C composite material, preparation method and application Download PDF

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CN115000387B
CN115000387B CN202210822412.8A CN202210822412A CN115000387B CN 115000387 B CN115000387 B CN 115000387B CN 202210822412 A CN202210822412 A CN 202210822412A CN 115000387 B CN115000387 B CN 115000387B
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composite material
heo
transition metal
carbon
spinel
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CN115000387A (en
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王健
孙胜银
杨亦双
胡学平
杨庆亨
马紫峰
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Zhongxing Pylon Battery Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention provides a spinel type TM-HEO/C composite material, a preparation method and application thereof, and particularly relates to the technical field of sodium ion batteries. Dissolving nitrate of transition metal in water to obtain transition metal precursor solution; and (3) dropwise adding a carbon carrier aqueous solution into the transition metal precursor solution for reaction, removing water to obtain a semi-finished product of the negative electrode composite material, and carrying out microwave heating on the semi-finished product of the negative electrode composite material to obtain the spinel type TM-HEO/C composite material. The preparation method forms transition metal high entropy oxide on a carbon carrier. The carbon carrier absorbs microwaves and converts the microwaves into high temperature, and the three-dimensional hierarchical structure and the large specific surface area of the carbon carrier lead the transition metal precursor to be heated uniformly and have uniform particle sizes. The carbon support enhances the conductivity of the TM-HEO in the cell reaction. The preparation method is simple and quick, low in energy consumption and low in cost, is favorable for rapidly producing high-entropy oxide in a large scale, and has good cycling stability when used for sodium ion batteries.

Description

Spinel type TM-HEO/C composite material, preparation method and application
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a spinel type TM-HEO/C composite material, a preparation method and application thereof.
Background
In recent years, transition metal-based high entropy oxide (TM-HEO) has attracted attention from battery researchers, which has stable structural entropy of crystal structure, higher specific capacity, excellent rate performance and cycle performance. However, at present, the TM-HEO is mostly prepared by a mechanical method and a high-temperature calcination method, the process repeatability and consistency of the methods are poor, the size of the obtained TM-HEO particles is difficult to control, and the element segregation is serious.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a preparation method of a spinel type TM-HEO/C composite material, which is used for relieving the defects of poor process repeatability and consistency of the preparation method of the TM-HEO in the prior art, difficult control of the size of the obtained TM-HEO particles and serious element segregation.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides a preparation method of a spinel type TM-HEO/C composite material, which comprises the steps of dropwise adding a carbon carrier aqueous solution into a transition metal precursor solution for reaction, removing water to obtain a semi-finished product of the cathode composite material, and carrying out microwave heating on the semi-finished product of the cathode composite material to obtain the spinel type TM-HEO/C composite material.
Optionally, the transition metal comprises at least five of Cr, mn, fe, co, ni, cu and Zn.
Preferably, the transition metals are Mn, fe, co, ni and Cu.
Preferably, the nitrate of the transition metal is dissolved in water to obtain the transition metal precursor solution.
Optionally, the mass concentration of each transition metal in the transition metal precursor solution is 5mg/mL-15mg/mL, preferably 10mg/mL.
Optionally, the carbon carrier includes at least one of a carbon nano-box, a carbon nano-tube, a carbon paper and a carbon cloth, and is preferably a carbon nano-box.
Preferably, the concentration of the aqueous carbon support solution is 1mg/mL-5mg/mL.
Optionally, the power of the microwave is 600w-1200w.
Preferably, the time of the microwaves is 0.5min-5min.
Optionally, the spinel TM-HEO/C composite material has a content of each transition metal of 2wt.% to 10wt.%.
Optionally, using magnesium oxide as a template, depositing carbon source gas on the magnesium oxide template by using a vapor deposition method, and then etching away the magnesium oxide template by using dilute acid to obtain the carbon nano-box.
Optionally, the carbon source comprises acetone and/or benzene.
Preferably, the ratio of the mass of magnesium oxide to the volume of the carbon source is 0.2g/mL-2g/mL.
Preferably, the calcination temperature of the vapor deposition is 700-1000 ℃, and the calcination time of the vapor deposition is 1-2 h.
Preferably, the dilute acid comprises dilute sulfuric acid and/or dilute nitric acid.
Preferably, the concentration of the dilute acid is 0.5mol/L-2mol/L.
The second aspect of the invention provides the spinel type TM-HEO/C composite material prepared by the preparation method.
The third aspect of the invention provides the application of the spinel type TM-HEO/C composite material in sodium ion batteries.
Compared with the prior art, the invention has at least the following beneficial effects:
according to the preparation method provided by the invention, the transition metal high-entropy oxide is formed on the carbon carrier. The carbon carrier absorbs microwaves and converts the microwaves into high temperature, and the three-dimensional hierarchical structure and the large specific surface area of the carbon carrier lead the transition metal precursor to be heated uniformly and have uniform particle sizes. The carbon carrier enhances the conductivity of the TM-HEO in the battery reaction, and is beneficial to the performance of the TM-HEO. The preparation method is simple and quick, low in energy consumption and low in cost, and is beneficial to the rapid mass production of the high-entropy oxide.
The spinel type TM-HEO/C composite material provided by the invention has controllable and uniform particle size, and shows excellent performance when being used for a negative electrode of a sodium ion battery.
The spinel type TM-HEO/C composite material provided by the invention is applied to sodium ion batteries, and the prepared sodium ion battery is 0.5A.g -1 Is still kept to 452 mA.h.g. after 1000 circles of circulation under the current density of (2) -1 Is a capacity of (2); the rate performance is tested at 5 A.g -1 The temperature of the mixture is kept at 303 mA.h.g -1 Has good circulation stability.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is an XRD pattern of a TM-HEO/C composite prepared in example 1 of the present invention;
FIG. 2 is a graph showing the rate performance of the TM-HEO/C composite material prepared in example 1 of the present invention;
FIG. 3 is a graph showing the cycle performance of the TM-HEO/C composite material prepared in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. The components of embodiments of the present invention may be arranged and designed in a wide variety of different configurations.
The development of clean energy has been increasingly emphasized due to the problems faced by energy crisis and environmental deterioration. In the current scientific energy storage method, the lithium ion battery is the most promising chemical energy storage power supply due to the advantages of high specific energy, low self-discharge, good cycling stability, no memory effect and the like. Although lithium ion batteries are considered as important products for achieving sustainable development of energy, alternative systems for lithium ion batteries must be found from the viewpoint of sustainable development of energy due to limited lithium resources on earth and uneven distribution (mainly in south america).
The sodium element is very abundant in the crust compared to the lithium element, about 422 times that of lithium. Sodium is the second light alkali metal next to lithium, and belongs to the same main group as lithium, and has an oxidation-reduction potential (Na + Na) is only 0.3V higher than lithium, thusHas similar electrochemical properties to lithium. Based on this, sodium ion batteries (NIBs) are the most desirable alternatives to LIBs.
Graphite has gained considerable attention as a commercial negative electrode material for lithium ion batteries. However, the unstable thermodynamic properties limit their use in sodium ion batteries. Therefore, a great deal of research work is being done, and it is urgent to find a suitable negative electrode material for sodium ion batteries, however, electrode materials which can be practically applied and have development value are still very limited due to the influence of the radius of sodium ions. At present, the negative electrode material of the sodium ion battery mainly comprises carbon-based materials, titanium-based materials, alloying materials, organic matters and the like, and is increasingly important for exploring novel negative electrode materials of the sodium ion battery. High entropy materials refer to materials with more than five alloying elements, which are typically prepared by a process that rapidly cools the material in the molten state. In recent years, transition metal-based high-entropy oxide (TM-HEO) has a crystal structure with stable configurational entropy, higher specific capacity and excellent rate capability and cycle performance. However, the research of TM-HEO is basically focused on the research of the cathode material of the lithium ion battery, and the cathode material is less used for the sodium ion battery, and is mostly prepared by a mechanical method and a high-temperature calcination method, and the methods have the problems of poor process repeatability and consistency, difficult control of the particle size of the material, serious element segregation and the like.
According to the preparation method of the spinel type TM-HEO/C composite material provided by the first aspect of the invention, a carbon carrier aqueous solution is dripped into a transition metal precursor solution for reaction, water is removed to obtain a semi-finished product of the cathode composite material, and the semi-finished product of the cathode composite material is subjected to microwave heating to obtain the spinel type TM-HEO/C composite material.
According to the preparation method provided by the invention, the transition metal high-entropy oxide is formed on the carbon carrier. The carbon carrier absorbs microwaves and converts the microwaves into high temperature, and the three-dimensional hierarchical structure and the large specific surface area of the carbon carrier lead the transition metal precursor to be heated uniformly and have uniform particle sizes. The carbon carrier enhances the conductivity of the TM-HEO in the battery reaction, and is beneficial to the performance of the TM-HEO. The preparation method is simple and quick, low in energy consumption and low in cost, and is beneficial to the rapid mass production of the high-entropy oxide.
AB 2 O 4 Spinel (AB) 2 O 4 ) In this crystal structure, oxygen ions are arranged in cubic close packing, divalent cations are filled in one eighth of tetrahedral voids, and trivalent cations are filled in one half of octahedral voids. Can dope a plurality of cations and simultaneously pair AB 2 O 4 Various physical properties of the spinel-type oxide are adjusted to meet the requirements of the anode material. By changing AB 2 O 4 The element composition of the A site and the B site in the structure increases the element type to improve the configuration entropy of the spinel-type oxide, and if the configuration entropy is high enough, a high-entropy spinel-type oxide material is formed.
Optionally, the transition metal comprises at least five of Cr, mn, fe, co, ni, cu and Zn.
Preferably, the transition metals are Mn, fe, co, ni and Cu.
Mn, fe, co, ni and Cu have larger specific capacity, have close element radius, are more uniformly distributed in the high-entropy oxide, have higher mixed entropy and are favorable for the stable existence of a high-entropy single-phase mixed system.
Preferably, the nitrate of the transition metal is dissolved in water to obtain the transition metal precursor solution.
Optionally, the mass concentration of each transition metal in the transition metal precursor solution is 5mg/mL-15mg/mL, preferably 10mg/mL.
When the mass concentration of each transition metal is less than 5mg/mL, the TM-HEO proportion in the composite material is lower, so that the capacity is lower; when the mass concentration of each transition metal is more than 15mg/mL, the carbon ratio in the composite material is too low, the conductivity of the material is reduced, and the rate performance is affected.
In some embodiments of the invention, the mass concentration of each transition metal is typically, but not limited to, 5mg/mL, 6mg/mL, 7mg/mL, 8mg/mL, 9mg/mL, 10mg/mL, 11mg/mL, 12mg/mL, 13mg/mL, 14mg/mL, or 15mg/mL.
Optionally, the carbon carrier includes at least one of a carbon nano-box, a carbon nano-tube, a carbon paper and a carbon cloth, and is preferably a carbon nano-box.
Preferably, the concentration of the aqueous carbon support solution is 1mg/mL-5mg/mL.
Optionally, the power of the microwave is 600w-1200w.
Preferably, the time of the microwaves is 0.5min-5min.
Optionally, the spinel TM-HEO/C composite material has a content of each transition metal of 2wt.% to 10wt.%.
The content of each transition metal is less than 2wt.%, the content of the produced high entropy oxide in the carbon support is low, resulting in a low specific capacity; the content of each transition metal is higher than 10wt.%, that is, the nitrate content is high, and decomposition is incomplete on the carbon nano-cartridge, and high entropy oxide cannot be formed completely.
In some embodiments of the present invention, the content of each transition metal is typically, but not limited to, 2wt.%, 3wt.%, 4wt.%, 5wt.%, 6wt.%, 7wt.%, 8wt.%, 9wt.%, or 10wt.%.
Optionally, using magnesium oxide as a template, depositing carbon source gas on the magnesium oxide template by using a vapor deposition method, and then etching away the magnesium oxide template by using dilute acid to obtain the carbon nano-box.
Optionally, the carbon source comprises acetone and/or benzene.
Preferably, the ratio of the mass of magnesium oxide to the volume of the carbon source is 0.2g/mL-2g/mL.
When the ratio of the mass of the magnesium oxide to the volume of the carbon source is lower than 0.2g/mL, the carbon layer is thinner, the structure is easy to collapse and unstable; when the ratio of the mass of magnesium oxide to the volume of the carbon source is higher than 2g/mL, the template is difficult to remove, and the cleaning time is long and the template is easy to remain.
In some embodiments of the invention, the ratio of the mass of the carbon source to the volume of magnesium oxide is typically, but not limited to, 0.2g/mL, 0.4g/mL, 0.6g/mL, 0.8g/mL, 1g/mL, 1.2g/mL, 1.4g/mL, 1.6g/mL, 1.8g/mL, or 2g/mL.
Preferably, the calcination temperature of the vapor deposition is 700-1000 ℃, and the calcination time of the vapor deposition is 1-2 h.
Preferably, the dilute acid comprises dilute sulfuric acid and/or dilute nitric acid.
Preferably, the concentration of the dilute acid is 0.5mol/L-2mol/L.
When the concentration of the dilute acid is lower than 0.5mol/L, the template is not easy to remove; when the concentration of the dilute acid is higher than 2mol/L, the dilute acid is not easy to remove, the cost is high, and the environment is polluted.
In some embodiments of the invention, the concentration of the dilute acid is typically, but not limited to, 0.5, 0.7, 0.9, 1.1, 1.3, 1.5, 1.7, 1.9, or 2mol/L.
The spinel type TM-HEO/C composite material prepared by the preparation method provided by the second aspect of the invention.
The spinel type TM-HEO/C composite material provided by the invention has controllable and uniform particle size, and shows excellent performance when being used for a negative electrode of a sodium ion battery.
The spinel type TM-HEO/C composite material provided by the third aspect of the invention is applied to sodium ion batteries.
The spinel type TM-HEO/C composite material provided by the invention is applied to sodium ion batteries, and the prepared sodium ion batteries are 0.5-0.5A g -1 Is still kept at 452mA hg for 1000 cycles at current density -1 Is a capacity of (2); rate performance test at 5Ag -1 The mAh g is still kept at 303mAh -1 Has good circulation stability.
Some embodiments of the present invention will be described in detail below with reference to examples. The following embodiments and features of the embodiments may be combined with each other without conflict.
Example 1
The embodiment provides a spinel type TM-HEO/C composite material, which is prepared by the following steps:
1. weighing 0.5g of magnesium oxide, placing into a tube furnace, under the protection of Ar, raising the temperature to 800 ℃ at 10 ℃/min, introducing 2ml of acetone at the speed of 0.1ml/min, keeping the temperature at 800 ℃ for 1h, and naturally cooling to obtain MgO@C.
2. MgO@C and 1mol/L dilute sulfuric acid are mixed according to the following dilute sulfuric acid: mgO@C is added in a proportion of 1ml/mg, stirred for 10 hours, filtered by suction and repeated 3 times. And stirring and washing with deionized water, filtering, repeating for 3 times, and finally drying at 60 ℃ to obtain the carbon nano-box.
3. And uniformly mixing manganese nitrate, ferric nitrate, nickel nitrate, cobalt nitrate and copper nitrate solutions with mass concentrations of 10mg/ml to obtain a transition metal precursor solution. 100mg of the carbon nano-cartridge was added to 50ml of water to obtain an aqueous solution of the carbon nano-cartridge. And (3) dropwise adding the carbon nano-box aqueous solution into the transition metal precursor solution, and reacting at 60 ℃ while stirring until the water is completely evaporated. Placing 50mg of powder into a glass bottle, placing into a household microwave oven (rated power is 1200 w), and adopting medium-fire (800 w) microwave for 1min to obtain the spinel type TM-HEO/C composite material.
FIG. 1 shows XRD patterns of the obtained spinel type TM-HEO/C composite material, and it can be seen from FIG. 1 that TM-HEO has a spinel structure and CoFe 2 O 4 The structure is similar, and no other phases are generated, which indicates that the preparation method can not cause phase separation of the high-entropy alloy.
Example 2
The present embodiment provides a spinel TM-HEO/C composite material, which is different from embodiment 1 in that in step 3, the mass concentration of the solutions of manganese nitrate, ferric nitrate, nickel nitrate, cobalt nitrate, and copper nitrate are all 5mg/ml, and the rest steps and raw materials are the same as embodiment 1, and are not described here again.
Example 3
The present embodiment provides a spinel TM-HEO/C composite material, which is different from embodiment 1 in that in step 3, the mass concentrations of the solutions of manganese nitrate, ferric nitrate, nickel nitrate, cobalt nitrate and copper nitrate are all 15mg/ml, and the rest steps and raw materials are the same as embodiment 1, and are not described here again.
Example 4
The difference between the spinel TM-HEO/C composite material provided in this embodiment and that in embodiment 1 is that 50mg of the carbon nano-cartridge is added to 100ml of water in step 3 to obtain a carbon nano-cartridge aqueous solution, and the rest steps and raw materials are the same as those in embodiment 1, and are not described here again.
Example 5
The difference between the spinel TM-HEO/C composite material provided in this embodiment and that in embodiment 1 is that in step 3, 150mg of the carbon nano-cartridge is added into 20ml of water to obtain an aqueous solution of the carbon nano-cartridge, and the rest steps and raw materials are the same as those in embodiment 1, and are not described here again.
Example 6
The present example provides a spinel type TM-HEO/C composite material, which is different from example 1 in that 0.25ml of acetone is introduced in step 1, and the rest steps and raw materials are the same as in example 1, and are not described here again.
Comparative example 1
The comparative example provides a spinel type TM-HEO material, wherein manganese nitrate, ferric nitrate, nickel nitrate, cobalt nitrate and copper nitrate solution with mass concentration of 10mg/ml are uniformly mixed to obtain a transition metal precursor solution, and the transition metal precursor solution is stirred at 60 ℃ until water is completely evaporated. Placing 50mg of powder into a glass bottle, placing into a household microwave oven (rated power 1200 w), and microwave with medium fire (800 w) for 1min to obtain spinel type TM-HEO material.
Experimental example 1
The materials obtained in examples 1 to 6 and comparative example 1 were subjected to electrochemical performance test.
The method comprises the following steps: assembling the materials into button half cell in glove box, using metal sodium sheet as counter electrode, containing 1.0M NaClO 4 And a Propylene Carbonate (PC) solution of 5.0% fec was used as the electrolyte.
The negative electrode takes N-methyl pyrrolidone (NMP) as a solvent, 80wt% of spinel type TM-HEO/C composite material or spinel type TM-HEO material, 10wt% of acetylene black and 10wt% of vinylidene fluoride (PVDF) are uniformly mixed, coated on copper foil, placed in a vacuum drying box, dried in vacuum for 24 hours at 80 ℃, cooled naturally to room temperature, placed on a roller press for rolling, the pole piece is tightly attached to the copper foil, cut into 14mm wafers through a cutting machine, weighed, then placed in a vacuum glove box, and half battery assembly is carried out. And standing for 24 hours at room temperature after the assembly, and carrying out electrochemical test after the electrolyte is completely soaked, wherein the obtained rate performance data and the obtained cycle performance data are shown in table 1.
Table 1 electrochemical test data sheet.
FIG. 2 is a graph showing the rate performance of the spinel type TM-HEO/C composite material prepared in example 1 as a negative electrode, when the current density was increased to 5Ag in the rate performance test -1 At the time, it still has 303mAh g -1 The good rate performance is derived from the good conductivity of the carbon nano-box, which is beneficial to the transmission of electrons.
FIG. 3 is a graph of the cycle performance of the TM-HEO/C composite prepared in example 1 at 0.5mA g -1 The reversible specific capacity after 1000 circles of circulation under the current density is still kept at 452mAh g -1 The excellent stability is due to the stability of the structure of the high entropy material itself.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims (11)

1. A preparation method of a spinel type TM-HEO/C composite material is characterized by dissolving nitrate of transition metal in water to obtain a transition metal precursor solution, wherein the mass concentration of each transition metal in the transition metal precursor solution is 10mg/mL; dropwise adding a carbon carrier aqueous solution with the concentration of 1mg/mL-5mg/mL into a transition metal precursor solution for reaction, removing water to obtain a semi-finished product of the negative composite material, and carrying out microwave heating on the semi-finished product of the negative composite material to obtain the spinel type TM-HEO/C composite material;
the power of the microwaves is 600w-1200w, and the time is 0.5min-5min;
the transition metals are Mn, fe, co, ni and Cu;
the spinel TM-HEO/C composite material has a content of each transition metal of 2wt.% to 10wt.%.
2. The method of manufacturing according to claim 1, wherein the carbon carrier comprises at least one of a carbon nano-box, a carbon nano-tube, a carbon paper, and a carbon cloth.
3. The method of claim 1, wherein the carbon support is a carbon nano-cassette.
4. The method according to claim 3, wherein the carbon nano-box is obtained by using magnesium oxide as a template, depositing a carbon source gas on the magnesium oxide template by a vapor deposition method, and etching away the magnesium oxide template by a dilute acid.
5. The method of claim 4, wherein the carbon source comprises acetone and/or benzene.
6. The method according to claim 4, wherein the ratio of the mass of magnesium oxide to the volume of the carbon source is 0.2g/mL-2g/mL.
7. The method according to claim 4, wherein the calcination temperature of the vapor deposition is 700 ℃ to 1000 ℃ and the calcination time of the vapor deposition is 1h to 2h.
8. The method of claim 4, wherein the dilute acid comprises dilute sulfuric acid and/or dilute nitric acid.
9. The process according to claim 4, wherein the concentration of the diluted acid is 0.5mol/L to 2mol/L.
10. A spinel TM-HEO/C composite material prepared by the method of any one of claims 1-9.
11. Use of the spinel TM-HEO/C composite material according to claim 10 in sodium ion batteries.
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